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Soluble material and process for three-dimensional modeling

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Publication number
CN101027170A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
composition
base polymer
soluble
dimensional
polymer
Prior art date
Application number
CN 200580031972
Other languages
Chinese (zh)
Inventor
威廉姆·R·小普列德埃曼
安德烈·L·布罗斯
Original Assignee
斯特拉塔西斯公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3Use of inorganic ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 to C08K5/59
    • C08K5/0016Plasticisers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39Particular shaping techniques, e.g. moulding, joining; Apparatus therefor
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/08Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39Particular shaping techniques, e.g. moulding, joining; Apparatus therefor
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34Component parts, details or accessories; Auxiliary operations
    • B29C41/36Feeding the material on to the mould, core or other substrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39Particular shaping techniques, e.g. moulding, joining; Apparatus therefor
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34Component parts, details or accessories; Auxiliary operations
    • B29C41/50Shaping under special conditions, e.g. vacuum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39Particular shaping techniques, e.g. moulding, joining; Apparatus therefor
    • B29C67/00Shaping techniques not covered by groups B29C39/00 to B29C65/00, B29C70/00 or B29C73/00
    • B29C67/0051Rapid manufacturing and prototyping of 3D objects by additive depositing, agglomerating or laminating of plastics material, e.g. by stereolithography or selective laser sintering
    • B29C67/0055Rapid manufacturing and prototyping of 3D objects by additive depositing, agglomerating or laminating of plastics material, e.g. by stereolithography or selective laser sintering using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39Particular shaping techniques, e.g. moulding, joining; Apparatus therefor
    • B29C67/00Shaping techniques not covered by groups B29C39/00 to B29C65/00, B29C70/00 or B29C73/00
    • B29C67/0051Rapid manufacturing and prototyping of 3D objects by additive depositing, agglomerating or laminating of plastics material, e.g. by stereolithography or selective laser sintering
    • B29C67/0085Apparatus components, details or accessories
    • B29C67/0092Support structures for the 3D object during manufacture, e.g. using sacrificial material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2003Use of starch or derivatives as moulding material
    • B29K2055/00Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K23/00 to B29K49/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2003Use of starch or derivatives as moulding material
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0008Anti-static agents

Abstract

The present invention is a composition for making a three-dimensional object. The composition comprises a plasticizer and a base polymer, where the base polymer comprises a carboxylic acid, where the composition is soluble in an alkaline solution.

Description

可溶性材料和用于三维造型的方法 Soluble materials and methods for three-dimensional modeling

技术领域 TECHNICAL FIELD

本发明涉及利用添加法造型技术制造三维物体。 The present invention relates to a method of adding modeling technology to produce three-dimensional objects. 更具体地,本发明涉及在构建物体时通过将可固化材料沉积成预定图案并向三维物体的支撑部提供支撑结构来形成这种三维物体。 More particularly, the present invention relates to build the object by depositing the curable material into a predetermined pattern to provide three-dimensional object supporting portion formed in a structure that supports three-dimensional objects.

背景技术 Background technique

添加法造型机基于从计算机辅助设计(CAD)系统提供的设计数据,通过构建造型介质制造三维模型。 Additive process modeling based on machine design data from computer-aided design (CAD) system provided by constructing a three-dimensional model molding medium manufacturing. 三维模型用于的功能包括审美判断、验证数学CAD模型、形成坚硬的工具、研究干扰及空间分配、以及测试功能性。 Features include three-dimensional model for the aesthetic judgment, to verify the mathematical CAD model, forming hard tool to study the interference and space allocation, and testing functionality. 一个技术是根据从CAD系统提供的设计数据,通过构建形成模型的多层将可固化的造型材料沉积成预定图案。 Is a technology based on design data from CAD system by constructing a multi-layer model of the formation of a curable molding material is deposited in a predetermined pattern.

Crump的美国专利第5,121,329号、Batchelder等人的美国专利第5,303,141号、Crump的美国专利第5,340,433号、Batchelder等人的美国专利第5,402,351号、Danforth等人的美国专利第5,738,817号、Batchelder等人的美国专利第5,764,521号以及Swanson等人的美国专利第6,004,124号中描述了用于通过从挤出头沉积多层可固化造型材料来制造三维模型的设备和方法的实例,所述的所有专利都转让给作为本发明受让人的明尼苏达州的Eden Prairie的斯特拉塔西斯公司。 U.S. Patent No. 5,121,329 Crump U.S. Patent No. 5,738,817, U.S. Patent No. 5,402,351, U.S. Patent No. 5,303,141 Batchelder et al., U.S. Patent No. 5,340,433 Crump's, Batchelder et al., Danforth et al., Batchelder et al. U.S. Patent No. 5,764,521 and U.S. Patent No. 6,004,124 Swanson et al., described for instance by depositing a multilayer extrusion head from the curable molding material to manufacture apparatus and method for three-dimensional model, all of the patents are for sale as to the assignee of the present invention Minnesota Eden Prairie company Xstrata Sith. 造型材料可以以固体形式(例如,以缠绕在供带盘(supply reel)上的柔性纤丝形式或者以实心杆形式)供应到挤出头,如美国专利第5,121,329号中所披露。 Molding material can be in solid form (for example, wound around the supply reel (supply reel) on flexible filaments form or in the form of a solid bar) supplied to the extrusion head, as disclosed in U.S. Patent No. 5,121,329. 如美国专利第4,749,347号中所述,造型材料可以可供选择地以液体形式从蓄液池抽出。 U.S. Patent No. 4,749,347 in the modeling material may alternatively in liquid form extracted from the fluid reservoir. 在任何情况下,挤出头都会从喷嘴将熔融的造型材料挤出到基底上。 In any case, the extrusion head from the nozzle will shape the molten material is extruded onto the substrate. 挤出的材料一层接一层地沉积在CAD模型所限定的区域中。 The extruded material is deposited layer by layer in the CAD model defined area. 在固化时通过充分的粘结粘附到前一层的可固化材料用作造型材料。 Adequate adhesion when cured by a layer bonded to the front of the curable material as a molding material. 己发现热塑性材料尤其适用于这些沉积造型技术。 The thermoplastic material has been found particularly suitable for these deposition modeling techniques.

例如,在Helinski的美国专利第5,136,515号、Masters的美国专利第4,665,492号和Masters的美国专利第5,216,616号中描述了用于通过沉积来自喷头的可固化材料来制造三维模型的设备和方法的实例。 For example, in Helinski U.S. Patent No. 5,136,515, U.S. Patent No. 4,665,492 and the Masters of U.S. Patent No. 5,216,616 Masters are described for instance by depositing a curable material from the nozzle apparatus and method for producing a three-dimensional model. 颗粒以CAD模型所限定的预定图案被引导至特定位置处并沉积及构建,以构造所需物体。 Particles defined by the CAD model is guided to a predetermined pattern and deposited at a specific location and build, to construct the desired object.

在通过添加法技术产生三维物体中,例如,通过沉积多层可固化材料产生三维物体中,这是惯例但不排除支撑层或结构在构造中必须用于悬空部分下或用于物体的凹槽内,从而不直接由造型材料本身进行支撑。 In generating three-dimensional objects by additive process techniques, e.g., by depositing multiple layers of the curable material to produce a three-dimensional object, which is usual, but does not preclude the supporting layers or structures it must be used in a suspended configuration for an object or a recess portion inside so as not to be directly supported by the modeling material itself. 例如,如果物体为地下洞穴内部的模型,并且洞穴原型是从地板朝着天花板进行构造的,则钟乳石将需要临时支撑直到完成天花板为止。 For example, if the object is inside the underground cave model, and the cave prototype is constructed from the floor towards the ceiling, the stalactite will require a temporary support until the ceiling is completed so far. 支撑层或结构因其它原因还需要,例如,使模型可以从基底移走、抵抗模型在部分完成时发生变形的趋势、以及通过构造过程抵抗施加到部分完成的模型的力。 Supporting layers or structures required for other reasons, e.g., so that the model can be removed from the base, to resist deformation model occurs when partially completed trends, as well as resistance to the force applied to a partially completed model by the construction process.

支撑结构可以利用与沉积造型材料相同的沉积技术和设备进行构建。 The support structure may be using the same deposition modeling material deposition technology and equipment to build. 该设备,在适当的软件控制下,制造用作用于正形成的物体的悬空或自由空间区段的支撑结构的另外几何形状。 The apparatus, under appropriate software control, manufacturing geometry used for additional support structure suspended or free-space segments of the object being formed. 支撑材料(support material)从造型设备内的单独的分配头进行沉积,或者通过与沉积造型材料相同的分配头进行沉积。 Support material (support material) deposited from a separate dispensing head within the modeling apparatus, or by the same deposition modeling material dispensing head deposition. 选择支撑材料,以使其可粘附到造型材料上。 Select the support material, so that it can adhere to the modeling material. 将模型固定到这种支撑结构上解决了构建模型中的问题,但是产生了在不造成模型损坏的情况下将支撑结构从完成的模型移走的另外的问题。 This model will be fixed to the support structure to build the model to solve the problem, but created another problem without causing damage to the model of the support structure removed from the finished model.

通过在模型与支撑结构之间形成不牢固且可破坏的粘结已解决移走支撑结构的问题,例如在Crump等人的美国专利第5,503,785号中所述。 Through between the model and the support structure is not solid and breakable bond formation has been resolved removal of the support structure issues, such as described in U.S. Patent No. 5,503,785 Crump et al. ′785专利披露一种方法,由该方法,将与造型材料形成不坚固且可破坏的粘结的材料选择为释放材料(release material)。 '785 patent discloses a method, by this method, not strong and can damage the adhesive material will form and shape the material selection for the release material (release material). 释放材料以层状方式或作为涂层沿着在物体与其支撑结构之间的界面沉积,使得支撑结构在物体成形之后可以脱离。 Release material as a coating or layer-wise deposited along the interface between the object and its support structure, the support structure such that after molding the object can be disengaged. 支撑结构可以由造型材料形成,或者所述支撑结构可以由释放材料形成。 The support structure may be formed by a molding material, the support structure may be formed by a material or the release.

′785专利披露可以用作造型及释放材料的各种材料组合。 '785 patent discloses the material can be used for modeling and release a variety of material combinations. 例如,′785专利披露了可以使用可溶性释放材料,使得保持在模型上的任何这种材料在支撑脱离之后可以通过将模型放置在浴槽内进行移除。 For example, the '785 patent discloses the release of soluble material can be used, so as to maintain the model of any such material after the support from the model can be placed in the bath for removal. 披露了水溶性蜡、聚环氧乙烷和二醇基聚合物、聚烯吡咯烷酮基聚合物、甲基乙烯基醚、马来酸基聚合物、聚噁唑啉基聚合物和聚季鎓II(polyquaternium II)以及可溶于溶剂的丙烯酸酯以及硬脂酸类和壬二酸类。 Discloses a water-soluble wax, polyethylene oxide and glycol-based polymer, polyolefin-based polymer pyrrolidone, methyl vinyl ether, maleic acid-based polymer, oxazoline-based polymers and quaternary onium II (polyquaternium II) and a solvent-soluble acrylic type and stearic acid and azelaic acids. 可溶性支撑件可以消除在模型表面上形成伤痕,并且可以消除利用力来移除支撑件的需要。 Soluble support member may be formed to eliminate the scars on the surface of the model, and may eliminate the need to use force to remove support member.

在基于挤出的系统中,己实现在层中施加释放材料的一个变化,其中释放材料在构造中以短珠粒片段(称作“穿孔”)施加到支撑结构与模型之间。 In the extrusion-based systems, to achieve a change in release materials have been applied in the layer, wherein the release material is constructed to short fragments beads (referred to as "punch hole") is applied between the support structure and the model. 该穿孔通过限制与模型的接触而积减小支撑层的粘附性,以帮助移除脱离的支撑件。 The perforation by exposure limits and models and reduce product adhesion to the support layer to help remove from the support member.

持续地需要提供一种支撑结构,所述支撑结构无需施加力就从三维模型中脱离,并且将不会损坏模型的表面光洁度,并且进一步具有良好的机械强度并可与造型过程和造型材料相容。 Continuing need to provide a support structure, the support structure without the application of force is released from the three-dimensional model, and will not damage the surface finish of the model, and further has good mechanical strength and are compatible with the molding process and the molding material .

发明内容 SUMMARY

本发明涉及一种用于制造三维物体的组合物。 The present invention relates to a composition for producing three-dimensional object. 所述组合物包括增塑剂和基础聚合物,其中所述基础聚合物包括羧酸,并且其中所述组合物可溶于碱性溶液中。 The composition comprises a base polymer and a plasticizer, wherein the base polymer comprises a carboxylic acid, and wherein said composition is soluble in an alkaline solution.

本发明进一步涉及一种用于制造三维物体的组合物,其中所述组合物包括含有羧酸的聚合物。 The present invention further relates to a composition for producing three-dimensional object, wherein said composition comprises a carboxylic acid-containing polymer. 所述组合物可溶于碱性溶液中,并且在230℃在1.2千克的负载下根据ASTM D1238进行测试时表现出约10克/10分钟或更小的熔体流动指数。 The composition is soluble in an alkaline solution and at 230 ℃ under a load of 1.2 kg in a test based on ASTM D1238 exhibits about 10 g / 10 minutes or less, a melt flow index.

本发明进一步涉及一种制造三维物品的方法。 The present invention further relates to a method of manufacturing three-dimensional objects. 所述方法包括将组合物沉积到基底上,其中所述组合物包括从羧酸获得的基础聚合物并使所述组合物可固化。 Said method comprising the composition can be deposited onto a substrate, wherein the composition comprises a base polymer and said carboxylic acid obtained from the curable composition. 所述组合物可溶于碱性溶液中,并且在230℃在1.2千克的负载下根据ASTM D1238进行测试时表现出约10克/10分钟或更小的熔体流动指数。 The composition is soluble in an alkaline solution and at 230 ℃ under a load of 1.2 kg in a test based on ASTM D1238 exhibits about 10 g / 10 minutes or less, a melt flow index.

附图说明 BRIEF DESCRIPTION

图1是将本发明的碱溶性材料用作支撑结构,通过纤丝供给挤出设备所形成的模型的示意图;以及图2是图1的模型在实施本发明的方法中所使用的碱浴槽中的透视图(部分被剥离)。 1 is the alkali-soluble material of the present invention is used as a support structure, a schematic model of the device formed by filaments extruded is supplied; and Figure 2 is a model diagram alkaline bath in the method of the present invention used in the perspective view (partially peeled).

具体实施方式 detailed description

采用碱溶性热塑性材料的本发明的方法适用于三维造型系统中,其中所述三维造型系统沉积熔融造型材料,所述的熔融造型材料固化以形成物体。 Methods alkali-soluble thermoplastic material of the present invention is suitable for three-dimensional modeling system, in which the three-dimensional modeling system modeling deposited molten material, the molten material is solidified to form the shape of the object.

通过参考美国专利第5,121,329号和美国专利第6,004,124号中所披露类型的沉积造型系统来描述本发明,所述的专利通过引用而结合在此,如同全部列于本说明书中一样。 U.S. Patent Reference deposition modeling system of the type disclosed in U.S. Patent No. 5,121,329 and No. 6,004,124 by the present invention is described in the patent is incorporated herein by reference as if fully as listed in this specification. 在所述的实施例中,造型材料和支撑材料从挤出头一层接一层地沉积为大体连续的线料,并且以柔性纤丝的形式供应到挤出头。 In the illustrated embodiment, the modeling material and the support material layer by layer deposition from the extrusion head to a substantially continuous strand, and supplied as a flexible filament into the extrusion head. 本领域普通技术人员将会理解,本发明具有的优势为可以各种其它类型的造型机中实施,并且材料可以以可供选择的形式供应,例如液体、实心杆、粒料或粒状形式。 Those of ordinary skill in the art will appreciate that the present invention has the advantage that various other types can be implemented molding machine, and the material may be supplied in the form of choice, such as a liquid, a solid rod, pellet or granular form.

图1显示构建根据本发明的由支撑结构28支撑的模型26的挤出设备10。 Figure 1 shows the construction according to the present invention by a supporting structure 28 supporting the device model 26 of the extrusion 10. 挤出设备10包括挤出头12、材料接收基底14、纤丝供应绕线轴16以及控制器18。 Extrusion apparatus 10 includes an extrusion head 12, receiving the base material 14, filament supply spool 16 and a controller 18. 用于挤出设备10的适当系统的实例包括Stratasys FDM系统,例如,Stratasys FDM1650、Stratasys FDM2000、Stratasys FDMTitan、Stratasys FDMVantage以及Stratasys FDMMaxum;以及“DimensionSST 3D Printer”;所有系统均可从明尼苏达州的Eden Prairie的斯特拉塔西斯公司。 Suitable system for extruding device 10 include Stratasys FDM system, for example, Stratasys FDM1650, Stratasys FDM2000, Stratasys FDMTitan, Stratasys FDMVantage and Stratasys FDMMaxum; and "DimensionSST 3D Printer" ; all systems are available from the Minnesota Eden Prairie company Xstrata Sith.

挤出头12相对于在通直或Z方向上移动的基底14在X和Y方向上移动。 Extrusion head 12 with respect to the straight or Z direction of the substrate 14 is moved in the X and Y directions. 供应绕线轴16将柔性纤丝20供应到挤出头12。 Supply spool 16 the flexible filaments 20 supplied to the extrusion head 12. 纤丝20典型地遵循相当曲折的路径穿过挤出设备10,并且通过步进电机驱动的压紧辊(pinch roller)朝着挤出头12前进。 20 filaments typically follow fairly tortuous path through the extrusion device 10, and by a stepping motor driven pinch roller (pinch roller) towards the extrusion head 12 forward. 纤丝20在液化器22内熔化、由挤出头22运送。 20 filaments within the liquefier 22 melted, transported by the extrusion head 22. 液化器22将纤丝加热到略高于其凝固点的温度、使纤丝还原到熔融状态。 Liquefier 22 filament is heated to a temperature slightly above its freezing point, so that the filaments restored to a molten state. 熔融材料经由液化器22的孔口24被挤出到基底14上。 Molten material through the aperture 24 of the liquefier 22 is extruded onto the substrate 14.

所披露的实施例的挤出设备10不具有用于使熔融材料穿过孔口24的流动在完成一层或一段时停止的正压截止阀(positive cut-off valve)。 Extrusion equipment as disclosed in Example 10 of the molten material does not have to flow through the orifice 24 at the completion of a period of one or stopped positive shut-off valve (positive cut-off valve). 该流动是通过使纤丝20停止前进到挤出头12内而停止的。 The flow is halted by the filaments 20 to 12 within the extrusion head and stopped. 将熔融材料分配到基底14上的流动速率通过结合孔口尺寸和纤丝20前进到挤出头12内的速率来确定。 Assign the molten material to flow rate of 14 on the substrate through a combination of aperture size and the filaments 20 proceeds to the rate of 12 within the extrusion head to determine.

挤出头12的运动由控制器18控制,以便以多段和多层的形式将材料沉积到基底14上,以构建具有由所储存的CAD数据所确定的形状的三维模型26,并进一步随着构建所述三维模型而构建限定为物理支撑模型26的支撑结构28。 Movement of the extrusion head 12 controlled by the controller 18 so as to form a multi-layer and multi-deposition of material onto the substrate 14, to construct a three-dimensional model having a stored CAD data 26 determined shape, and further with Construction of the three-dimensional model is defined as physical support and to build a support structure model 26 28. 在具有受到控制以促进固化的环境的构建围护(build envelope)内,模型26及其支撑结构28在基底14上构建。 Having a controlled environment in order to promote the curing envelope construct (build envelope) within the model 26 and support structure 28 is built on a substrate 14. 第一层沉积材料粘附到基底上以形成基础,而后续材料层互相粘附。 Depositing a first layer of material adhered to the substrate to form the basis, and the subsequent layer of material adhered to each other. 已成功使用的基底为以可移走方式安装到工作台上的聚合物泡沫。 The substrate has been successfully used is to removably mounted to the table polymeric foam. 可以用作基底的其它材料包括由涂敷有砂的细线筛网形成并粘附到工作台上的砂纸、可溶于水的蜡、泡沫塑料材料、以及安装到真空压平板上的聚丙烯酸酯片材。 Other materials may be used as the substrate comprises sand coated with a thin mesh is formed and adhered on a worktable sandpaper, water-soluble wax, foam material, and a plate mounted to the vacuum pressure of polyacrylic acid esters sheet.

分配造型材料A以形成模型26。 A molding material to form a distribution model 26. 碱溶性支撑材料B配合造型材料A的分配进行分配以形成支撑结构28。 Alkali-soluble support material B with the allocation modeling material A is dispensed to form a support structure 28. 为了方便起见,挤出设备10仅显示具有一个提供单纤丝20的纤丝供应绕线轴16。 For convenience, the extrusion device 10 having a display only provide monofilament filament supply bobbin 20 16. 然而,应该理解的是在使用诸如在此所披露的纤丝供给设备的本发明的实施中,将造型材料A和碱溶性支撑材料B通过单独的纤丝供应绕线轴提供给挤出设备10。 However, it should be understood that in use, such as in the embodiment disclosed herein filament supply device of the present invention, the modeling material A and an alkali-soluble support material B through a separate supply bobbin filaments to the extrusion device 10. 挤出设备10因而可以容纳通过以下设置进行分配的两种不同的材料:(1)提供两个挤出头12,一个供应有造型材料A,一个供应有造型材料B(例如′124专利中所披露);(2)提供单个挤出头,所述单个挤出头通过用于分配两种材料的单一喷嘴供应有造型材料A和碱溶性支撑材料B两种材料(例如,′329专利的图6中所示);或者(3)提供供应有两种材料的单一挤出头,其中经由单独的喷嘴分配每种材料(例如′785专利的图6中所示)。 Extrusion apparatus 10 which can accommodate the following settings allocated by two different materials: (1) providing two extrusion heads 12, one supplied with modeling material A, is supplied with a molding material B (e.g., '124 patent disclosure); (2) providing a single extrusion head, the single extrusion head through a single nozzle for the distribution of the two materials supplied with the modeling material a and an alkali-soluble support material B two materials (for example, '329 patent FIG. FIG. 6); or (3) providing a single extrusion head supplied with both materials, wherein (e.g., '785 patent shown in Fig. 6) assigned for each material via a separate nozzle.

造型材料A典型地为热塑性材料,其可以相对快速地被从固态加热到高于材料的固化温度的预定温度,并且优选地具有相对较高的抗拉强度。 A molding material is typically a thermoplastic material, which may be from a solid state relatively quickly heated to above the curing temperature of the material of a predetermined temperature, and preferably has a relatively high tensile strength. 丙烯腈-丁二烯-苯乙烯(ABS)组合物为一种特别适当的造型材料。 Acrylonitrile - butadiene - styrene (ABS) composition is particularly suitable as a molding material. 可以用于造型材料A的其它材料包括各种蜡、石蜡、各种热塑性树脂、金属和金属合金。 Other materials may be used for the molding material A include various waxes, paraffin, various thermoplastic resins, metals and metal alloys. 包括两部分(two-part)环氧的玻璃和化学固化材料也将适用。 It consists of two parts (two-part) and chemically curing epoxy glass material will also apply.

本发明的碱溶性支撑材料B为可溶于碱性溶液的热塑性塑料,如以下更详细地说明。 Alkali-soluble support material B of the present invention is soluble in an alkaline solution of thermoplastics, described in more detail below. 碱溶性支撑材料B同样可以优选从固态纤丝相对快速地加热到高于材料固化温度的预定温度,并且当分配后通过温度下降而固化。 Alkali-soluble support material B can also be preferably filaments from the solid state relatively quickly heated to above the curing temperature of the material of a predetermined temperature, and when the temperature dropped and solidified by distribution.

通过支撑材料B产生的可溶解性支撑结构28可以以己知的方式形成,例如美国专利第5,503,785号中所披露,所述的专利通过引用而结合在此,如同全部列于本说明书中一样。 Generated by the soluble support material B may support structure 28 may be formed in known manner, e.g., as disclosed No. 5,503,785 U.S. Patent, the patent is incorporated herein by reference, as if fully as listed in the present specification. ′785专利的图3-5说明了一种可移除的支撑结构。 '785 patent Figures 3-5 illustrate a removable support structure. 如在此图1中所示,支撑结构28可以整体从支撑材料B中构建。 1 as shown in this figure, the support structure 28 may be integrally constructed from the support material B, respectively. 或者,如′785专利中所示及说明,碱溶性支撑材料B可以在由造型材料A形成的模型与由相同材料A形成的支撑结构之间形成可溶解的连接。 Or, as' 785 patent shown and described, the alkali-soluble support material B may be between model and support structure made of the same material A is formed by the molding material A soluble form to form. 该连接可以为一层或多层释放层(release layer)或者薄涂层。 The connection can be one or more layers of release layer (release layer) or a thin coating.

在完成模型26之后,通过将模型26与其连接的支撑结构28一起浸泡在含有碱性溶液C的浴槽40内,将支撑结构28从模型26移除。 After completion of the model 26, model 26 by the support structure 28 connected thereto together with a soak in the bath alkaline solution containing C 40, the support structure 28 is removed from the model 26. 在图2中所示的实施例中,浴槽40为含有用于保持模型26的可移走的网筐42的超声波的、温度受控槽。 In the embodiment shown in FIG. 2, the bath 40 containing the model 26 for holding removable mesh basket 42 of the ultrasonic wave, the temperature-controlled tank. 使用温度控制器44设定浴槽40的温度。 44 temperature controller set temperature bath 40. 碱性溶液C为可以从排液管冲掉以进行处理的水溶液。 C is the aqueous alkaline solution can be flushed from the discharge tube for processing. 可以加热浴槽40中的溶液C的温度以加快支撑材料B的溶解。 The temperature of the bath can be heated in a solution of 40 C to accelerate the dissolution of the support material B. 具有通/断开关的超声波频率产生器46开始及停止超声波传输。 Ultrasound has an on / off switch of the frequency generator 46 start and stop ultrasound transmission. 超声波频率传输产生气泡,所述的气泡通过使模型振动帮助溶解掉支撑材料B。 Ultrasonic frequency transmission bubbles, the bubbles by Shaking help dissolve the support material B.

模型26保持在浴槽40内直到支撑材料B溶解。 Model 26 maintained in the bath 40 until the support material B were dissolved. 网筐42接着被从浴槽40移走。 Net basket 42 is then removed from the bath 40. 可以将网筐42可以在水槽中,并且用水将溶液C从模型26冲洗掉并从排液管冲掉。 You can mesh baskets 42 may be in the sink, and rinse with water from the solution C Model 26 away from the discharge pipe and flush. 浴槽40具有排液管48,从排液管48中除去插塞以将溶液C从浴槽40排掉。 Bath 40 has a drain pipe 48 is removed from the discharge pipe 48 in the plug to the bath solution C from 40 to drain.

作为用于通过在浴槽内溶解碱溶性支撑材料B将支撑结构28从模型26移除的可供选择例,可以使用用手或自动操作的喷水器溶解支撑材料。 As by dissolving the alkali-soluble support material B in the bath will be removed from the support structure 28 models to choose from Example 26 can be used by hand or automatically operated sprinkler used to dissolve the support material.

基底14可以在将模型放置在浴槽40内之前从模型26移走。 Substrate 14 can be placed in the bath model 40 is removed from the model within the preceding 26. 可供选择地,基底14在将模型26放置在浴槽40内时可以保持粘附在模型26上。 Alternatively, when the substrate 14 is placed in the bath model 26 can be kept within 40 to adhere to the model 26. 在后一种情况中,可能需要碱溶性基底,例如,碱溶性泡沫。 In the latter case, the alkali-insoluble substrate may be required, for example, an alkali-soluble foam.

碱溶性支撑材料B必须满足用于使用其的特定造型系统的大量造型标准,大致涉及热性质、强度、粘度和粘附性。 Alkali-soluble support material B must be met for the use of its large number of specific modeling system modeling standards relates generally to thermal properties, strength, viscosity, and adhesion. 对于热性质,碱溶性支撑材料B在构建围护中的温度下不变形,以保持其支撑的模型的结构保真度。 For the thermal properties, alkali-soluble support material B is not deformed in the build envelope temperatures in order to maintain its support structure fidelity of the model. 因此需要碱溶性支撑材料B具有比构建围护温度至少高10℃的玻璃化转变温度(Tg)。 Requiring alkali-soluble support material B than building envelope having a temperature of at least 10 ℃ higher glass transition temperature (Tg). 进一步而言,如果碱溶性支撑材料B的玻璃化转变温度低于造型材料A的玻璃化转变温度,则通过温度控制,可以提高碱溶性支撑材料B的溶解速率。 Further, if the glass of the alkali-soluble support material B of the transition temperature lower than the glass transition temperature of the modeling material A, through temperature control, can increase the rate of dissolution of the alkali-soluble support material B.

碱溶性支撑材料B必须具有适用于造型过程的熔体粘度。 Alkali-soluble support material B must have a melt viscosity suitable for molding process. 在此处所述类型的造型系统中,熔体粘度在液化器的温度下必须足够低,使得所述支撑材料可以经由液化器的孔口作为大致连续的线料或珠粒挤出,使得沉积的碱溶性支撑材料B的线料或珠粒具有很小的熔体强度,从而可以将所述支撑材料平放而非卷起。 In the modeling system of the type described herein, the melt viscosity at the temperature of liquefaction must be low enough so that the support material can be used as a substantially continuous beads or strands extruded through the orifice of the liquefier, so that the deposition the alkali-soluble support material B having a small bead or strand of melt strength, so that the support material may be flat, rather than rolled up. 熔体粘度通过增加液化器中的温度而降低。 Melt viscosity by increasing the temperature of the liquefaction vessel is reduced. 然而,液化器的温度过高可以造成空闲搁置在液化器中的材料分解。 However, the liquefaction temperature is too high can cause decomposition of the material resting idle in liquefier. 如果分解,在挤出头不具有正压截止机构的情况下,支撑材料B将不受控制地从液化器排出到构建围护中,这种状态称作“渗漏”。 If you break down, in the case of the extrusion head does not have a positive closing mechanism, the support material B uncontrolled discharge from the liquefier to the build envelope, this state is called "leakage." 实际上,可以通过所述支撑材料的逆参数(熔体流动)测量粘度。 In fact, the viscosity can be measured by the inverse of the buttress material parameters (melt flow). 如在230℃在1.2kg的负载下根据ASTM D1238所测量的,对于碱溶性支撑材料B所需的熔体流动指数在约1g/10分钟与约10克/10分钟之间,并且优选在约5克/10分钟与约10克/10分钟之间。 As in 1.2kg at 230 ℃ measured under a load, according to ASTM D1238 for the alkali-soluble support material B in the desired melt flow index of between about 1g / 10 minutes and about 10 g / 10 minutes, and preferably from about 5 g / 10 min and about 10 g / 10 min.

为了在构建中适当地支撑模型,碱溶性支撑材料B必须粘结到其本身上(自层压(self-laminate))并较弱地粘结到造型材料A上(共层压(co-laminate))。 In order to build the appropriate support model, an alkali-soluble support material B must be adhered to on itself (self-laminating (self-laminate)) and weakly bonded to the molding material A (co-laminated (co-laminate )). 在从基底构建支撑结构的情况下,碱溶性支撑材料B必须另外粘结到基底14上。 In the case of the support structure constructed from the base, an alkali-soluble support material B must also be bonded to the substrate 14. 本发明的碱溶性支撑材料B中的酸含量使材料相当粘,使得所述支撑材料将会充分地粘附到由任何数量的材料制成的基底上。 Acid content of the alkali-soluble support material B of the present invention is that the material is quite sticky, so that the support material will be fully adhered to the substrate by any of a number of materials. 例如,已成功地uqf聚氨酯泡沫基底用于本发明的实施中。 For example, it has successfully uqf polyurethane foam substrate used in the practice of the present invention.

为了生产准确的模型,碱溶性支撑材料B在构建围护的条件中通过冷却还必须表现出很小的收缩,或者,收缩特征必须与造型材料A的收缩特征相匹配。 In order to produce an accurate model of the alkali-soluble support material B in the build envelope by cooling conditions they must also exhibit very little shrinkage, or contraction characteristics must match the shrinkage characteristics of modeling material A. 材料中的收缩差别将会沿着模型/支撑结构的连接处造成应力和粘结失效。 Shrinkage difference in the material will cause stress and bond failure along the model / support joint structure.

碱溶性支撑材料B在固体形式下必须具有足够的机械强度,以在模型的成形期间向模型提供支撑。 Alkali-soluble support material B in a solid form must have sufficient mechanical strength to the period of a mold to provide support to the model. 碱溶性支撑材料B必须抵抗造型材料A的力,否则模型将会表现出不受欢迎的卷曲和变形。 Alkali-soluble support material B must resist the force modeling material A, otherwise the model will exhibit unwanted curl and distortion. 另外,碱溶性支撑材料B在以纤丝或杆的形式进行供应时必须坚固到足以不会断开地进行运送。 Further, the alkali-soluble support material B when in the form of filaments or bar supply must be strong enough to not be shipped off to. 当以纤丝形式供应时,碱溶性支撑材料B必须进一步具有强度和柔性,以形成缠绕和退绕并经由挤出设备供给而不会断开的纤丝。 When the supply in the form of filaments, the alkali-soluble support material B must have the strength and flexibility further, to form a wound and unwound and fed via extrusion equipment without breaking the filaments. 同样地,以纤丝形式供应的碱溶性支撑材料B必须具有足够的刚性,以便在经由挤出设备供给期间不会因压缩力而变形。 Similarly, alkali-soluble support material B supplied in filament form must have sufficient rigidity so that the compressive force will not deform during extrusion apparatus via supply. 大约为1000-5000psi的抗拉强度典型地适于沉积造型应用中。 Tensile strength of about 1000-5000psi typically adapted for deposition modeling applications.

碱溶性支撑材料B所需的溶解性特征为,所述支撑材料容易溶解在不会不利地影响造型材料A的碱性溶液(pH7或更高)中。 Solubility characteristics alkali-soluble support material B is desired, the support material is easily dissolved without adversely affecting the molding material A basic solution (pH 7 or higher),. 如在此所使用,如果材料大体溶解和/或分散在具有约7或更高的pH以及范围从约25℃至约80℃的温度的溶液中,则材料为“可溶于碱性溶液中”。 As used herein, if the material is substantially dissolved and / or dispersed in having a pH of about 7 or higher and a solution temperature ranging from about 25 ℃ to about 80 ℃, the material is "soluble in an alkaline solution . " 另外还需要溶液无毒且不易燃,使得不需要使用者特别处理或处置。 It also needs a solution and not flammable, non-toxic, so users do not need special treatment or disposal.

本发明的碱溶性支撑材料B由基础聚合物组成,所述基础聚合物可以包括第一共聚单体(含有羧酸)、以及与第一共聚单体聚合(例如,通过自由基聚合)以提供适用于沉积造型的热性质和韧性性质的第二共聚单体。 Alkali-soluble support material B of the present invention consists of base polymer, the base polymer may comprise a first copolymerizable monomer (containing carboxylic acid), and the first and comonomers (e.g., by free radical polymerization) to provide the second comonomer suitable for deposition modeling of thermal properties and toughness properties. 合适的第二共聚单体是甲基丙烯酸烷基酯(包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯和甲基丙烯酸丁酯)、或多种甲基丙烯酸烷基酯的组合。 Suitable comonomers are second alkyl methacrylate (include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate), alkyl methacrylate, or more The combination. 可获得其中将使用碱溶性支撑材料B的造型系统所需的热特征和韧性特征的其它单体也可以用作第二共聚单体。 Which can be obtained using an alkali-soluble support material B modeling system for the thermal characteristics and toughness characteristics of other monomers may also be used as the second comonomer. 优选的基础聚合物由作为第一共聚单体的甲基丙烯酸和作为第二共聚单体的甲基丙烯酸甲酯组成。 Preferably the base polymer as a first comonomer and a second comonomer methacrylic acid methyl methacrylate monomer.

含酸的第一共聚单体的所需量为基础聚合物的15-60重量百分比。 Copolymerization of the desired amount of the first acid-containing monomer is 15-60 weight percent of the base polymer. 碱溶性支撑材料B的溶解性是由于基础聚合物中的羧酸。 Alkali-soluble support material B is due to the solubility of the carboxylic acid in the base polymer. 当基础聚合物的酸含量增加时,用于溶解所述支撑材料的碱性溶液的所需碱度(pH)减小。 When increasing the acid content of the base polymer for dissolving the alkalinity of alkaline solution required to support material (pH) decreases. 可选择地,另外的单体可以结合到基础聚合物中。 Optionally, additional monomers may be incorporated into the base polymer.

本发明的碱溶性支撑材料B还可以包括增塑剂,以获得造型过程所需的流变性质。 Alkali-soluble support material B of the present invention may further comprise a plasticizer, to obtain the desired rheological properties of the molding process. 适当的增塑剂的选择取决于许多因素。 Plasticizers suitable choice depends on many factors. 增塑剂必须将干燥的基础聚合物增塑成符合所需标准的适合加工的热塑性塑料。 Plasticizer must be dried by the base polymer molded thermoplastics conform to the required standards for processing. 另外,增塑剂必须与基础聚合物相容。 In addition, a plasticizer must be compatible with the base polymer. 相容性由极性、分散性和氢键合力决定,如8.0或更高(优选8.5或更高)的Small溶解度参数所示(利用Small摩尔吸引常数方法),或者如17.0(优选17.5或更高)的Hansen溶解度参数所示(来自CRCPress(1991)出版的Handbook of Solubility Parameters中所述的Hansen法)。 Compatibility is determined by the polarity of the resultant dispersion and hydrogen bonding, such as 8.0 or more (preferably 8.5 or higher) Small solubility parameter shown (use Small molar attraction constant method), or as 17.0 (preferably 17.5 or more H) Hansen solubility parameters shown Handbook (from CRCPress (1991) published by of solubility parameters in the method of Hansen). 增塑剂不能表现出以油膜形式渗漏到增塑的聚合物上。 Plasticizers can not show to film in the form of leaks to the plasticized polymer. 增塑剂在材料加工及造型温度下必须具有低蒸气压,优选地,其蒸气压在200℃小于10毫米汞柱而在250℃小于20毫米汞柱。 In the processing plasticizer and the molding material temperature must have a low vapor pressure, preferably at 200 ℃ vapor pressure of less than 10 mm Hg but less than 20 mm Hg at 250 ℃. 增塑剂另外必须可水解、可溶解、可乳化或可分散在为pH7或更高的碱溶剂化浴中。 Furthermore the plasticizer must be hydrolyzable, soluble, emulsifiable or dispersible in the alkali pH7 or more solvated bath.

增塑剂会减小粘度(即,增加熔体流动指数),还降低聚合物的玻璃化转变温度。 Plasticizer reduces the viscosity (i.e., increase in melt flow index), but also lower the glass transition temperature of the polymer. 同样地,碱溶性支撑材料B中的增塑剂的浓度理想地提供如上所述的所需的玻璃化转变温度和熔体流动指数。 Similarly, the concentration of alkali-soluble support material B desirably plasticizer described above to provide the desired glass transition temperature and melt flow index. 例如,热塑性可溶支撑材料B理想地表现出比构建围护温度至少高10℃的玻璃化转变温度。 For example, over the surface of the thermoplastic soluble support material B exhibits than building Retaining temperature of at least 10 ℃ high glass transition temperature. 同样地,碱溶性支撑材料B理想地表现出范围从约1克/10分钟至约10克/10分钟内(优选在5克/10分钟与10克/10分钟之间)的熔体流动指数。 In the same manner, the alkali-soluble support material B ideal demonstration of the range from about 1 g / 10 minutes to about 10 g / 10 min (preferably 5 g / 10 min and 10 g / 10 min between) a melt flow index .

碱溶性支撑材料B中的增塑剂的浓度可以取决于各种因素,例如用于造型材料A的材料、用于基础聚合物和碱溶性支撑材料B增塑剂的材料、构建围护温度、以及造型材料A和碱溶性支撑材料B所需的流动速率。 Concentration of the alkali-soluble support material B of the plasticizer may depend on various factors, such as the material for the molding material A, the base polymer and an alkali-soluble support material B plasticizer material for build envelope temperature, and modeling material a and an alkali-soluble support material B required flow rate. 碱溶性支撑材料B中的增塑剂的适当浓度的实例的范围基于碱溶性支撑材料B的总重量为约0.01重量%至约50重量%。 Alkali-soluble support material B range of the appropriate concentration of the plasticizer based on the total weight of the example of the alkali-soluble support material B is from about 0.01% to about 50 wt% by weight. 碱溶性支撑材料B中的增塑剂的特别适当的浓度实例的范围基于碱溶性支撑材料B的总重量从约5.0重量%至约25重量%。 Examples of particularly suitable concentration range of the alkali-soluble support material B, based on the total weight of the plasticizer alkali-soluble support material B range from about 5.0 wt% to about 25 wt%.

发现可相容的增塑剂包括以下通类的增塑剂:邻苯二甲酸二烷基酯、邻苯二甲酸环烷基酯、邻苯二甲酸苄酯和芳酯、邻苯二甲酸烷氧基酯、磷酸烷基酯/芳基酯、羧酸酯、聚乙二醇酯、己二酸酯、柠檬酸酯以及甘油酯。 Found compatible plasticizers include the following general classes of plasticizers: phthalic acid alkyl esters, cycloalkyl esters of phthalic acid, phthalic acid benzyl esters and aryl esters, alkyl phthalates alkoxy phosphate ester alkyl / aryl esters, carboxylic acid esters, polyethylene glycol esters, adipate esters, citrate esters and glycerol. 具有发现可相容的特定结构的可商购增塑剂包括:乙酸酯:乙酸枯基苯酯;甘油三乙酸酯、三醋精;己二酸酯:己二酸二(丁氧基乙氧基乙)酯己二酸二(丁氧基乙)酯己二酸二异丁酯柠檬酸酯:柠檬酸三正乙酯乙酰柠檬酸三正乙酯柠檬酸三正丙酯乙酰柠檬酸三正丙酯柠檬酸三正丁酯; Commercially available plasticizer has found to be compatible with a specific structure include: acetate: acetic acid cumyl phenyl; triacetin, triacetin; adipate: adipic (butoxy ethoxyethyl) ester of adipic acid di (butoxy ethyl) esters of adipic acid diisobutyl citrate: citric acid, acetyl tri-ethyl citrate tri-ethyl citrate tri-n-propyl acetyl citrate tri-n-propyl TBC;

乙酰柠檬酸三正丁酯;邻苯二甲酸酯:DBP,邻苯二甲酸二丁酯(部分相容性);BBP,邻苯二甲酸丁苄酯(完全相容性);DBEP邻苯二甲酸二丁氧基乙酯(部分相容性);邻苯二甲酸二乙基己苄酯;邻苯二甲酸四甲基氧杂壬(onononyl)苄酯;苯甲酸酯:二苯甲酸二丙二醇酯;二苯甲酸二乙二醇酯;50/50混合的二苯甲酸二丙二醇酯与二苯甲酸二乙二醇酯;二苯甲酸-1,4-环己烷二甲醇酯甘油三苯甲酸酯;苯甲酸枯基苯酯;二苯甲酸新戊二醇酯;季戊四醇四苯甲酸酯;磷酸酯:磷酸丁苯二苯酯;TCP,磷酸三甲苯酯;磷酸二(乙基己)二苯酯;磷酸异癸二苯酯;磷酸C12、C16烷二苯酯;异丙基化的磷酸三苯酯;聚二醇:聚乙二醇类;聚丙二醇类; Acetyl Tributyl Citrate; phthalate: DBP, dibutyl phthalate (partial compatibility); BBP, phthalate, butyl benzyl phthalate (full compatibility); DBEP phthalic dicarboxylate butoxyethyl (partial compatibility); diethylhexyl phthalate benzyl ester; tetramethylammonium phthalate oxanonandiamine (onononyl) benzyl; benzoate: dibenzoate dipropylene glycol; diethylene glycol dibenzoate ester; 50/50 blend of dipropylene glycol dibenzoate and diethylene glycol dibenzoate ester; 1,4-cyclohexane dimethanol dibenzoate esters of glycerol tri benzoate; cumyl phenyl benzoate; neopentyl glycol dibenzoate; pentaerythritol tetra-benzoate; phosphate: SBR diphenyl phosphate; TCP, tricresyl phosphate; phosphate, di (ethyl hexyl) diphenyl carbonate; dibutyl phosphate isopropyl phenyl ester; phosphoric acid C12, C16 alkyl diphenyl; of isopropyl triphenyl phosphate; polyethylene glycol: polyethylene glycol; polypropylene glycols;

特别优选的增塑剂具有高热稳定性,并且包括:磷酸对叔-丁基苯二苯酯;邻苯二甲酸丁苄酯;邻苯二甲酸-7-(2,6,6,8-四甲基-4-氧杂-3-氧代壬)苄酯;邻苯二甲酸C7/C9烷苄酯;磷酸2-乙基己二苯酯;以及磷酸异癸二苯酯。 A particularly preferred plasticizer has high thermal stability, and includes: t-phosphatase - butylphenyl diphenyl phosphate; phthalate, butyl benzyl phthalate; phthalate-7- (2,6,6,8- four methyl-4-oxa-3-oxo-nonyl) benzyl ester; phthalic C7 / C9 alkyl benzyl ester; 2-ethylhexyl diphenyl phosphate; and phosphoric acid phenyl ester isopropyl sebacate.

可选择地,碱溶性支撑材料B可以含有其它成分,例如填充材料。 Alternatively, alkali-soluble support material B may contain other ingredients, such as filler material. 例如,惰性填料可以从由碳酸钙、碳酸镁、玻璃球体、石墨、炭黑、碳纤维、玻璃纤维、滑石、硅灰石、云母、氧化铝、硅石、高岭土、晶须和碳化硅构成的聚合物填料组中进行选择。 For example, the polymer may be inert fillers, calcium carbonate, magnesium carbonate, glass spheres, graphite, carbon black, carbon fibers, glass fibers, talc, wollastonite, mica, alumina, silica, kaolin, silicon carbide whiskers, and from packing group to choose. 也可以使用无机填料,例如可溶性盐。 The inorganic filler may be used, such as soluble salts.

聚合物化学中的传统技术用于将组成材料混合成碱溶性支撑材料B。 Polymer chemistry of conventional techniques for the composition of the material mixed into an alkali-soluble support material B. 该配方可以成型为杆状、粒料或其它形状以用于挤出设备中,或者可以直接用于所述设备中而无需进行之前的固化。 The formulation may be shaped as a rod, pellets or other shapes for use in extrusion equipment, or the equipment may be used directly and without prior curing. 可供选择地,混合物可以固化并接着成粒状,用以以粒状形式供应到挤出设备。 Alternatively, the mixture may be solidified into a granular shape and then, in particulate form to be supplied to the extrusion apparatus. 为了用于在本说明书所示及说明的造型过程中,将粒状进料组合物通过传统的挤出设备进行加工以形成连续的柔性纤丝。 For use in the molding process as shown and described in the present specification, the processing granular feed composition by conventional extrusion equipment to form a continuous flexible filaments. 理想地,这些纤丝以连续长度缠绕在卷绕轴上并进行干燥。 Ideally, a continuous length of these filaments wound on the winding shaft and dried. 将呈纤丝形式的碱溶性支撑材料B供应到如上所述的挤出设备10。 Will show the filaments in the form of an alkali-soluble support material B is supplied to the extrusion apparatus 10 described above. 纤丝20典型地为大约0.070英寸的非常小的直径,并且直径可以小到0.001英寸。 20 filaments typically about 0.070 inches in a very small diameter, and the diameter can be as small as 0.001 inches.

实例在以下实例中更具体地说明本发明,其中由于在本发明的范围内的许多修改和变更对本领域普通技术人员是显而易见的,因此所述实例仅是作为说明。 Examples In the following examples further illustrate the present invention, in which as many modifications and variations within the scope of the present invention to those of ordinary skill is obvious, therefore the examples are only by way of illustration. 除非另外注释,以下实例中所提出的所有份、百分比和比率都是以重量为基础的,并且实例中所使用的所有试剂均从一般的化学制品供应商(例如,密苏里州的圣路易斯的Sigma-Aldrich Chemical Company)获得或可购得,或者可以通过传统技术合成。 Unless otherwise noted, all parts, percentages and ratios set forth in the following examples are on a weight basis, and all reagents used in the examples are from the general chemical suppliers (for example, St. Louis, Missouri of Sigma- Aldrich Chemical Company) to obtain or commercially available, or can be synthesized by conventional techniques.

实例I碱溶性热塑性材料含有74%的基础聚合物和26%的磷酸丁苯二苯酯增塑剂。 Examples I alkali-soluble thermoplastic material containing 74% of the base polymer and 26% phosphoric acid diphenyl butadiene plasticizer. 基础聚合物由甲基丙烯酸和甲基丙烯酸甲酯的较高及较低分子量共聚物的组成。 The higher the base polymer and a lower molecular weight copolymer of methacrylic acid and methyl methacrylate components. 基础聚合物大致含有50%的较高分子量共聚物和50%的较低分子量共聚物,每一个加上或减去5%。 Base polymer containing approximately 50% of the high molecular weight copolymer and 50% of the lower molecular weight copolymers, each plus or minus 5%. 各共聚物含有1∶2重量百分比的甲基丙烯酸与甲基丙烯酸甲酯。 Each copolymer contains 1:2 weight percent of methacrylic acid and methyl methacrylate. 较高分子量共聚物的特征为高粘度(低熔体流动),较低分子量共聚物的特征为低粘度(高熔体流动)。 Higher molecular weight copolymer is characterized by a high viscosity (low melt flow), wherein the lower molecular weight copolymer has a low viscosity (high melt flow). 通过分别对具有26重量百分比的磷酸丁苯二苯酯增塑剂的各共聚物进行增塑,测量共聚物的熔体流动。 By separately for each butadiene copolymer diphenyl phosphate having 26 percentage by weight of a plasticizer plasticized, measurement of melt flow of the copolymer. 如在230℃在1.2千克的负载下根据ASTM D1238所测量,已增塑的高分子量共聚物的熔体流动指数在0.4克/10分钟至0.8克/10分钟的范围内。 230 ℃ as measured in accordance with ASTM D1238 under a load of 1.2 kg, the melt flow index of the high molecular weight copolymer is plasticized in a range of 0.4 g / 10 to 0.8 minutes / 10 minutes. 已增塑的低分子量共聚物的熔体流动指数在28克/10分钟至35克/10分钟的范围内。 It has a melt flow index of the low molecular weight copolymer plasticized in the range of 28 g / 10 to 35 minutes / 10 minutes. 所得到的热塑性组合物具有5克/10分钟至6.5克/10分钟的熔体流动指数以及约90℃的玻璃化转变温度。 The resulting thermoplastic composition having 5 g / 10 to 6.5 minutes / 10 minutes and a melt flow index of the glass transition temperature of about 90 deg.] C.

碱溶性热塑性材料被加工成0.070英寸直径的纤丝并缠绕在卷绕轴上。 Alkali-soluble thermoplastic material is processed into a diameter of 0.070 inches and filament wound winding shaft. 纤丝被供给到Stratasys FDM1650或Stratasys FDM2000台式造型机。 Stratasys FDM1650 filaments is fed to a desktop or Stratasys FDM2000 molding machine. 将熔融的碱溶性热塑性材料从具有200℃温度的液化器挤出到70℃的构建围护内至聚氨酯泡沫基底上。 The molten alkali-soluble thermoplastic material has a temperature of from 200 ℃ liquefier extruded to construct the envelope 70 ℃ polyurethane foam to the substrate. 挤出的碱溶性热塑性材料具有约0.020英寸至约0.040英寸的路宽(road width)和约0.007英寸至约0.020英寸的路高(薄片间隔)。 Extruded alkali-soluble thermoplastic material has about 0.020 inches to about 0.040 inches lane (road width) of about 0.007 inches to about 0.020 inches high road (sheet interval). 通过使用用于形成支撑件的碱溶性热塑性材料,由具有104℃的玻璃化转变温度的ABS热塑性塑料构建模型。 By using the supporting member for forming the alkali-soluble thermoplastic materials by having a glass transition temperature of 104 ℃ ABS thermoplastics build the model. 具有连接的支撑件的模型被放置在超声波清洗浴槽(具有25-27赫兹的扫描频率)内,其中所述超声波清洗浴槽容纳有约98.7重量百分比的水、0.85重量百分比的水软化剂、0.30重量百分比的pH调节剂以及0.15重量百分比的表面活性剂的碱性水溶液,从而得到11至13的pH。 Having a support member connected to the model is placed in an ultrasonic cleaning bath (having a scanning frequency of 25-27 Hertz), wherein the ultrasonic cleaning bath accommodating water of about 98.7 weight percent, 0.85 weight percent of the water softener, 0.30 wt. the percentage of the pH adjusting agent and a basic aqueous solution of a surfactant of 0.15 weight percent, whereby pH. 11 to 13. 浴槽的温度被设定成70℃(浴槽的温度必须保持低于造型材料A的玻璃化转变温度)。 The temperature of the bath is set to (bath temperature must be kept below the glass transition temperature of the modeling material A) 70 ℃. 在两个小时或更少的时间内,支撑件被溶解。 Within two hours or less time, the support is dissolved.

可供选择的基础聚合物配方将甲基丙烯酸和甲基丙烯酸甲酯的较高分子量的1∶2共聚物与含有40%的甲基丙烯酸和60%的甲基丙烯酸丁酯的较低分子量共聚物相组合。 Alternative base polymer formulation of the higher molecular weight methacrylic acid and methyl methacrylate 2 copolymer containing 40% methacrylic acid and 60% of the lower molecular weight butyl methacrylate copolymer phase combinations. 进一步可供选择的基础聚合物配方将丙烯酸用作第一共聚单体。 Further alternative formulations based acrylic polymer used as the first comonomer. 然而,所述进一步可供选择被发现对于应用于StratasysFDM造型机中是不能接受的,这是因为其会造成基础聚合物具有低于机器的构建围护温度的较低玻璃化转变温度。 However, the further options have been found to apply to StratasysFDM molding machine is not acceptable, since it will cause the base polymer has a lower temperature envelope machine Construction of low glass transition temperature.

实例II Example II

碱溶性热塑性材料含有79%(+/-5%)的基础聚合物和21%(+/-5%)的磷酸丁苯二苯酯增塑剂。 Alkali-soluble thermoplastic material contains 79% (+/- 5%) of base polymer and 21% (+/- 5%) of phosphoric acid diphenyl ester plasticizer-butylbenzene. 基础聚合物由1∶1重量百分比的甲基丙烯酸与甲基丙烯酸甲酯组成,并具有135,000克/摩尔的分子量。 1:1 the base polymer weight percent of methacrylic acid and methyl methacrylate, and having a 135,000 g / mol molecular weight. 在基础聚合物与增塑剂相混合之前,基础聚合物在220℃炉内以低压进行加热以除去聚合物中的水。 Before the base polymer is mixed with a plasticizer, the base polymer at 220 ℃ low pressure furnace for heating the polymer to remove water. 发现以低压加热10-15小时足以干燥基础聚合物。 Found that low pressure heating 10-15 hours sufficient drying of the base polymer. 获得的干燥聚合物呈粒状形式,从而以己知的方式与增塑剂一起供给到配混机内。 The polymer obtained was dried particulate form so as to have known the way with a plasticizer supplied together within the compounder. 如在230℃在1.2千克的负载下根据ASTM D1238所测量,获得的可溶于碱性热塑性材料具有在5克/10分钟至6.5克/10分钟的范围内的熔体流动指数。 230 ℃ as measured in accordance with ASTM D1238 under a load of 1.2 kg, a thermoplastic material soluble in alkaline is obtained having in the range of 5 g / 10 to 6.5 minutes / 10 minutes of melt flow index. 碱溶性热塑性材料的玻璃化转变开始温度约为101.5℃,而玻璃化转变峰值温度约为111℃。 Alkali-soluble thermoplastic material has a glass transition onset temperature of about 101.5 ℃, and a glass transition peak temperature of about 111 ℃.

如上述的实例I中,碱溶性热塑性材料被加工成0.070英寸直径的纤丝并缠绕在卷绕轴上。 As described above in Example I, the alkali-soluble thermoplastic material is processed into a diameter of 0.070 inches and filament wound winding shaft. 纤丝被供给到Stratasys FDM1650或Stratasys FDM2000台式造型机。 Stratasys FDM1650 filaments is fed to a desktop or Stratasys FDM2000 molding machine. 将熔融的碱溶性热塑性材料从具有235℃温度的液化器挤出到70℃至80℃的构建围护内至聚氨酯泡沫基底上。 The molten alkali-soluble thermoplastic material has a temperature of from 235 ℃ liquefier extruded deg.] C to 70 deg.] C to construct the envelope 80 to the polyurethane foam substrate. 挤出的碱溶性热塑性材料具有约0.020英寸至0.040英寸的路宽和约0.007英寸至约0.020英寸的路高(薄片间隔)。 Extruded alkali-soluble thermoplastic material of about 0.020 to 0.040 inches and about 0.007 inches to the lane is about 0.020 inches high road (sheet interval). 通过使用用于形成支撑件的碱溶性热塑性材料由具有104℃的玻璃化转变温度的ABS热塑性塑料构建模型。 By using the supporting member for forming the alkali-soluble thermoplastic material it is made of a glass having a transition temperature of 104 ℃ ABS thermoplastics build the model. 为了使支撑件溶解,模型被放置在设定为70℃且具有25-27赫兹的扫描频率的超声波清洗浴槽内,其中所述超声波清洗浴槽容纳有约98.7%的水、0.85%的水软化剂、0.30%的pH调节剂以及0.15%的表面活性剂的碱性水溶液。 In order to dissolve the support member, the model is placed in a set of 70 ℃ 25-27 Hz and has a scanning frequency of the ultrasonic cleaning bath, wherein the ultrasonic cleaning bath accommodating water of about 98.7%, 0.85% water softener , 0.30% of a pH adjusting agent and 0.15% of an alkaline aqueous solution of a surfactant. 在两个小时或更少的时间内,支撑件被溶解。 Within two hours or less time, the support is dissolved. 根据这个实例的碱溶性热塑性材料表现出适用于在Stratasys纤丝供给台式机上进行三维造型的热性质、机械强度、粘度、粘附性、可溶性以及加工特征。 According to this example, the alkali-soluble thermoplastic material exhibits suitable for three-dimensional modeling in Stratasys supplied to the filaments on the desktop thermal properties, mechanical strength, viscosity, adhesion, solubility and processing characteristics.

实例III碱溶性热塑性材料与上述的实例II具有相同的组成,但是在这个实例中,基础聚合物未被加热来释放湿气。 Example III above alkali-soluble thermoplastic materials of Examples II and have the same composition, but in this example, the base polymer is not heated to release moisture. 碱溶性热塑性材料如在实例II中被加工并从Stratasys FDM机器挤出,并且沉积以形成用于ABS热塑性塑料所构建的模型的支撑结构。 Alkali-soluble thermoplastic material is processed as in Example II and extruded from Stratasys FDM machine, and the deposition to form a support structure for ABS thermoplastics constructed model. 在这个实例中,碱溶性热塑性材料表现出自挤出头比理想更大量的“渗漏”,但是另外表现出适用于三维造型的特征。 In this example, the performance of the alkali-soluble thermoplastic material from the extrusion head over a larger amount than the "leakage", but additional exhibits characteristics suitable for three-dimensional modeling. “渗漏”可归因于组合物中存在的水。 "Leakage" is attributable to the presence in the composition in water. 如果应用于其中材料分配器具有正压截止机构的造型系统中,则Stratasys FDM机器中所表现出的“渗漏”效果将不会发生,并且可以有效地利用根据这个实例III的材料。 If the material is used in which the dispenser has a positive cutoff mechanism modeling system, the Stratasys FDM machines exhibited "leakage" effect will not occur, and can be effectively utilized according to the material of this Example III.

实例IV通过改变增塑剂的浓度产生本发明的碱溶性热塑性材料的样品,以比较增塑剂对玻璃化转变温度和熔体流动指数的影响。 IV Examples of plasticizers produced by changing the concentration of the alkali-soluble thermoplastic material sample of the present invention to compare the plasticizer glass transition temperature and melt flow index. 所使用的基础聚合物和增塑剂与实例I中所述的相同。 In the same base polymer and a plasticizer as used in Example I. 表1提供实例IV(A)-实例IV(M)的碱溶性热塑性材料的重量百分比浓度。 Table 1 provides examples IV (A) - Examples of weight percent concentration IV (M) of the alkali-soluble thermoplastic material. 如所示,增塑剂的浓度在所述样品之间进行变化。 As shown, the concentration of the plasticizer between the sample changes. 表1还提供实例IV(A)-实例IV(M)的碱溶性热塑性材料的相应的玻璃化转变温度(Tg)和熔体流动指数(MFI)。 Table 1 provides further examples IV (A) - Examples of appropriate glass IV (M) of the alkali-soluble thermoplastic material transition temperature (Tg) and melt flow index (MFI). 在160℃、230℃或270℃在1.2千克的负载下根掘ASTM D1238测试熔体流动指数。 At 160 ℃, 230 ℃ or 270 ℃ under a load of 1.2 kg in roots dug melt flow index ASTM D1238 test.

表1 Table 1

(*)基于碱溶性热塑性材料的总重量。 (*) An alkali-soluble thermoplastic material based on the total weight.

表1中的数据说明增塑剂浓度对碱溶性热塑性材料的玻璃化转变温度和熔体流动指数的影响。 Table 1 data show that the concentration of plasticizer transition temperature and melt flow index of glass alkali-soluble thermoplastic material. 通常,当碱溶性热塑性材料中的增塑剂的浓度增加时,玻璃化转变温度降低而熔体流动指数增加。 Typically, when the concentration of the alkali-soluble thermoplastic material plasticizer, the glass transition temperature is lowered and the melt flow index increases. 同样地,改变增塑剂的浓度提供玻璃化转变温度与熔体流动指数之间的平衡。 Similarly, changing the concentration of plasticizer provided between the glass transition temperature and the melt flow index of balance.

对于用于实例IV(A)-实例IV(M)的基础聚合物和增塑剂,范围从约49℃(45%增塑剂)至约160℃(无增塑剂)的玻璃化转变温度通常与增塑剂的浓度成反向线性。 Examples of the IV (A) - Examples IV (M) of the base polymer and a plasticizer, ranges from about 49 ℃ (45% plasticizer) to about 160 ℃ (no plasticizer), a glass transition temperature usually associated with the concentration of plasticizer to reverse linear. 如上所述,本发明的碱溶性支撑材料理想地表现出比构建围护温度至少高10℃的玻璃化转变温度。 As described above, the alkali-soluble support material over the surface of the present invention exhibit than building Retaining temperature of at least 10 ℃ high glass transition temperature. 同样地,当使用高构建围护温度(例如,100℃或更高)时,具有低浓度的增塑剂的碱溶性热塑性材料是优选的(例如,25%或更少),使碱溶性热塑性材料表现出较高的玻璃化转变温度。 Alkali-soluble thermoplastic material in the same manner, when using high build envelope temperatures (e.g., 100 deg.] C or higher), having a low concentration of plasticizer are preferred (e.g., 25% or less), the alkali-soluble thermoplastic the material exhibits a high glass transition temperature.

就230℃所测试的熔体流动指数而言,表1中的数据显示熔体流动指数大致以指数方式相对于增塑剂的浓度增加。 The melt flow index of 230 ℃ tested on, the data in Table 1 show a melt flow index of approximately exponentially increased with respect to the concentration of plasticizer. 增塑剂从25%增加到35%造成熔体流动指数从约6克/10分钟增加到约35克/10分钟。 Plasticizers cause a melt flow index from 25 per cent to 35 per cent from about 6 g / 10 min to about 35 g / 10 min. 如上所述,优选范围从约1克/10分钟至约10克/10分钟的熔体流动指数。 As described above, preferably in the range from about 1 g / 10 minutes to about 10 g / 10 min melt flow index. 同样地,约6克/10分钟的熔体流动指数认为是用于挤出材料的可接受的条件。 Similarly, about 6 g / 10 min melt flow index is considered acceptable conditions for the extruded material. 然而,约35克/10分钟的熔体流动指数可能造成所需的物理性质潜在地下降。 However, about 35 grams / 10 minutes melt flow index of the desired physical properties can cause potentially decrease.

如表1中所示,约25%或更少的增塑剂浓度(实例IV(A)-实例IV(K))提供约100℃或更高的玻璃化转变温度,以及提供在230℃的约6克/10分钟的熔体流动指数。 As shown in Table 1, about 25% or less of the concentration of plasticizer (Example IV (A) - Examples IV (K)) to provide about 100 deg.] C or higher glass transition temperature, and provided at the 230 ℃ about 6 g / 10 min melt flow index. 这种增塑剂浓度为本发明的碱溶性热塑性材料提供可接受的物理特征。 Alkali-soluble thermoplastic materials of the present invention this concentration of plasticizer to provide acceptable physical characteristics.

尽管已参考优选实施例说明了本发明,然而本领域普通技术人员将会意识到在不偏离本发明的本质和范围的前提下可以做形式及细节上的变更。 Despite reference to preferred embodiments illustrate the present invention, however, one of ordinary skill in the art will realize that without departing from the spirit and scope of the present invention can be provided in the form and details of the changes. 例如,将理解可以对造型过程进行无数修改。 For example, the shape can be understood that numerous modifications process. 将进一步理解可以对组合物进行各种修改。 Will be further understood that various modifications of the compositions. 同样,本发明的热塑性材料可以用于产生在各种造型过程中均有效的碱溶性三维物体。 Similarly, the thermoplastic material of the present invention can be used to produce a variety of shapes that are valid during the alkali-soluble three-dimensional object. 例如,碱溶性材料在流延或注射过程中可以形成可溶解的主芯体。 For example, alkali-soluble material in the casting or injection process and form soluble core main body. 碱溶性材料同样可以用于产生模型(通过沉积造型或其它方式),该模型稍后可以从造型过程中所形成的物体中溶解出。 Alkali-soluble materials may also be used to generate the model (by deposition modeling or otherwise), object modeling from the model can later be formed during the dissolving out.

Claims (38)

1.一种用于制造三维物体的组合物,所述组合物包括增塑剂和基础聚合物,所述基础聚合物包括羧酸,其中所述组合物可溶于碱性溶液中。 1. A method for producing three-dimensional object in the composition, the composition comprising a plasticizer and a base polymer, the base polymer comprises a carboxylic acid, wherein said composition is soluble in an alkaline solution.
2.根据权利要求1所述的组合物,其中所述增塑剂基于所述组合物的总重量占所述组合物的重量的约0.01%至约50.0%。 2. The composition according to claim 1, wherein said plasticizer based on the total weight of the composition comprises from about 0.01% to about 50.0% by weight of said composition.
3.根据权利要求2所述的组合物,其中所述增塑剂基于所述组合物的总重量占所述组合物的重量的约5.0%至约25.0%。 The composition according to claim 2, wherein said plasticizer based on the total weight of the composition comprises from about 5.0% to about 25.0% by weight of said composition.
4.根据权利要求1所述的组合物,其中所述增塑剂选自:由磷酸对-叔丁基苯二苯酯;邻苯二甲酸丁苄酯;邻苯二甲酸-7-(2,6,6,8-四甲基-4-氧杂-3-氧代壬)苄酯;邻苯二甲酸C7/C9烷苄酯;磷酸-2-乙基己二苯酯;磷酸异癸二苯酯及其组合组成的组中。 4. The composition according to 1, wherein said plasticizer is selected from claim: phosphoric acid - tert - butylphenyl diphenyl phosphate; phthalate, butyl benzyl phthalate; phthalate 7- (2 , 6,6,8- tetramethyl-4-oxa-3-oxo-nonyl) benzyl ester; phthalic C7 / C9 alkyl benzyl ester; 2-ethylhexyl diphenyl phosphate; phosphate, isodecyl diphenyl group, and combinations thereof.
5.根据权利要求1所述的组合物,其中所述羧酸包括甲基丙烯酸。 5. The composition of claim 1, wherein said carboxylic acid comprises methacrylic acid.
6.根据权利要求5所述的组合物,其中所述羧酸基于所述基础聚合物的总重量占所述基础聚合物的重量的约15.0%至约60.0%。 6. A composition according to claim 5, wherein said carboxylic acid based on the total weight of the base polymer comprises from about 15.0% to about 60.0% by weight of the base polymer.
7.根据权利要求1所述的组合物,其中所述基础聚合物进一步包括甲基丙烯酸烷基酯。 7. The composition of claim 1, wherein said base polymer further comprises an alkyl methacrylate.
8.根据权利要求7所述的组合物,其中所述甲基丙烯酸烷基酯包括甲基丙烯酸甲酯。 The composition according to claim 7, wherein the alkyl methacrylate include methyl methacrylate.
9.根据权利要求1所述的组合物,其中所述组合物表现出范围从约49℃至约160℃的玻璃化转变温度。 9. The composition of claim 1, wherein the composition exhibits range from the glass about 49 ℃ to about 160 ℃ transition temperature.
10.根据权利要求1所述的组合物,其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出范围从约1克/10分钟至约10克/10分钟的熔体流动指数。 10. The composition of claim 1, wherein when at 230 ℃ under a load of 1.2 kg according to ASTM D1238 when tested, the composition exhibits range from about 1 g / 10 minutes to about 10 g / 10 minute melt flow index.
11.根据权利要求10所述的组合物,其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出范围从约5克/10分钟至约10克/10分钟的熔体流动指数。 11. The composition of claim 10, wherein when at 230 ℃ under a load of 1.2 kg according to ASTM D1238 when tested, the composition exhibits range from about 5 g / 10 minutes to about 10 g / 10 minute melt flow index.
12.一种用于制造三维物体的组合物,所述组合物包括含有羧酸的聚合物,其中所述组合物可溶于碱性溶液中,并且其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出约10克/10分钟或更小的熔体流动指数。 12. A method for producing three-dimensional object in the composition, the composition comprises a carboxylic acid-containing polymer, wherein the composition is soluble in an alkaline solution, and wherein when at 230 ℃ under a load of 1.2 kg when tested in accordance with ASTM D1238, the composition exhibits about 10 g / 10 minutes or less, a melt flow index.
13.根据权利要求12所述的组合物,进一步包括增塑剂。 13. The composition of claim 12, further comprising a plasticizer.
14.根据权利要求13所述的组合物,其中所述增塑剂基于所述组合物的总重量占所述组合物的重量的约25.0%或更少。 14. The composition of claim 13, wherein said plasticizer based on the total weight of the composition comprises about 25.0% of the composition by weight or less.
15.根据权利要求12所述的组合物,其中所述组合物表现出约100℃或更高的玻璃化转变温度。 15. The composition of claim 12, wherein the composition exhibits about 100 ℃ or higher glass transition temperature.
16.根据权利要求12所述的组合物,其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出范围从约5克/10分钟至约10克/10分钟的熔体流动指数。 16. The composition of claim 12, wherein when at 230 ℃ under a load of 1.2 kg according to ASTM D1238 when tested, the composition exhibits range from about 5 g / 10 minutes to about 10 g / 10 minute melt flow index.
17.根据权利要求12所述的组合物,其中所述羧酸包括甲基丙烯酸。 17. The composition of claim 12, wherein said carboxylic acid comprises methacrylic acid.
18.根据权利要求12所述的组合物,其中所述基础聚合物进一步包括甲基丙烯酸烷基酯。 18. The composition of claim 12, wherein said base polymer further comprises an alkyl methacrylate.
19.根据权利要求18所述的组合物,其中所述甲基丙烯酸烷基酯包括甲基丙烯酸甲酯。 19. The composition of claim 18, wherein the alkyl methacrylate include methyl methacrylate.
20.根据权利要求18所述的组合物,其中所述羧酸基于羧酸和甲基丙烯酸烷基酯的总重量占羧酸和甲基丙烯酸烷基酯重量的约15.0%至约60.0%。 20. The composition of claim 18, wherein said carboxylic acid and carboxylic acid based on the total weight of the alkyl methacrylate comprises about 15.0% to about 60.0% acid and alkyl methacrylate by weight.
21.根据权利要求18所述的组合物,其中所述羧酸和所述甲基丙烯酸烷基酯被聚合。 21. The composition of claim 18, wherein said carboxylic acid and said alkyl methacrylate is polymerized.
22.一种制造三维物品的方法,所述方法包括:沉积包括从羧酸获得的基础聚合物的组合物,其中所述组合物可溶于碱性溶液,并且其中当在230℃在1.2于克的负载下根据ASTM D1238进行测试时,所述组合物表现出约10克/10分钟或更小的熔体流动指数;以及使所述组合物固化。 22. A method of producing a three-dimensional object, the method comprising: depositing a composition comprising a base polymer derived from a carboxylic acid, wherein said composition is soluble in an alkaline solution, and wherein when at 1.2 to 230 ℃ g under a load in accordance with ASTM D1238 test time, the composition exhibits about 10 g / 10 minutes or less, a melt flow index; and allowing the composition to cure.
23.根据权利要求22所述的方法,其中以多个步骤沉积及固化所述组合物以制造多层,其中所述层限定所述三维物品。 23. The method according to claim 22, wherein the step of depositing a plurality of, and curing the composition to produce a multi-layer, wherein said layer defines the three-dimensional object.
24.根据权利要求22所述的方法,其中所述组合物进一步包括增塑剂。 24. The method according to claim 22, wherein said composition further comprises a plasticizer.
25.根据权利要求24所述的方法,其中所述增塑剂基于所述组合物的总重量占所述组合物重量的约25.0%或更少。 25. The method according to claim 24, wherein said plasticizer based on the total weight of the composition comprises about 25.0% of the composition by weight or less.
26.根据权利要求24所述的方法,其中所述组合物沉积在表现出构建围护温度的构建围护内,并且其中所述增塑剂在所述组合物中被浓缩成有效水平,以使所述组合物表现出高于所述构建围护温度的玻璃化转变温度。 26. The method of claim 24, wherein said composition is deposited on the build envelope temperatures exhibited the build envelope, and wherein said plasticizer in said composition is concentrated to a level effective to so that the composition exhibits the build envelope temperatures higher than the glass transition temperature.
27.根据权利要求24所述的方法,其中所述增塑剂基于所述组合物的总重量占所述组合物重量的约25.0%或更少。 27. The method according to claim 24, wherein said plasticizer based on the total weight of the composition comprises about 25.0% of the composition by weight or less.
28.根据权利要求27所述的方法,其中所述组合物表现出约100℃或更高的玻璃化转变温度。 28. The method of claim 27, wherein the composition exhibits about 100 ℃ or higher glass transition temperature.
29.根据权利要求27所述的方法,其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出范围从约5克/10分钟至约10克/10分钟的熔体流动指数。 29. The method according to claim 27, wherein when at 230 ℃ under a load of 1.2 kg according to ASTM D1238 when tested, the composition exhibits range from about 5 g / 10 minutes to about 10 g / 10 min the melt flow index.
30.根据权利要求22所述的组合物,其中所述羧酸包括甲基丙烯酸。 30. The composition of claim 22, wherein said carboxylic acid comprises methacrylic acid.
31.根据权利要求22所述的组合物,其中进一步从甲基丙烯酸烷基酯获得所述基础聚合物。 31. The composition of claim 22, wherein said base polymer is further obtained from an alkyl methacrylate.
32.根据权利要求31所述的组合物,其中所述甲基丙烯酸烷基酯包括甲基丙烯酸甲酯。 32. The composition of claim 31, wherein the alkyl methacrylate include methyl methacrylate.
33.在一种用于制造三维物体的方法中,所述方法是通过将可固化造型材料分配成预定图案以限定所述三维物体,结合分配可固化支撑材料以限定用于所述三维物体的支撑结构,来制造所述三维物体,所述支撑结构从而具有与所述物体相接触的部分,其改进包括:至少所述支撑结构与所述物体接触的部分由包括含有羧酸的聚合物的热塑性材料形成,其中所述组合物可溶于碱性液体,并且其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出约10克/10分钟或更小的熔体流动指数。 33. In a method for manufacturing a three-dimensional object, the method is obtained by molding the curable material is dispensed into a predetermined pattern to define the three-dimensional object, integrating the distribution of curable material to define a support for said three-dimensional object a support structure, the manufactured three-dimensional object, whereby the support structure has a portion in contact with said object, the improvement comprising: at least the support structure and the object contacts a portion of the carboxylic acid containing polymer comprising the the thermoplastic material, wherein said composition is soluble in an alkaline liquid, and wherein when at 230 ℃ under a load of 1.2 kg in accordance with ASTM D1238 test time, the composition exhibits about 10 g / 10 minutes or less the melt flow index.
34.根据权利要求33所述的方法,其中所述热塑性材料进一步包括基于所述热塑性材料的总重量占所述热塑性材料重量的约0.01%至约50.0%的增塑剂。 34. The method according to claim 33, wherein the thermoplastic material further comprises based on the total weight of the thermoplastic material of the thermoplastic material comprises from about 0.01% by weight to about 50.0% of a plasticizer.
35.一种用于制造三维物体的添加方法,该方法包括:将碱溶性造型材料分配成预定图案,以限定具有在成形期间需要支撑的悬空部的三维物体;以及将支撑材料分配到所述三维物体的悬空部下方的空间内,结合所述造型材料的分配,以形成用于所述物体的三维支撑结构,所述支撑材料包括含有羧酸的聚合物,其中所述组合物可溶于碱性溶液,并且其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出约10克/10分钟或更小的熔体流动指数;由此使所述支撑材料通过施加碱性溶液从所述三维物体溶解掉。 35. A method for producing three-dimensional objects is added, the method comprising: assigning an alkali-soluble material into a predetermined shape pattern, to define a three-dimensional object having a vacant portion during the forming of the required support; and assigned to the support material the space below the suspended portion of the three-dimensional object, in combination with the distribution of molding material to form a three-dimensional support structure for the object, said support material comprises a polymer containing a carboxylic acid, wherein said composition is soluble alkaline solution, and wherein when at 230 ℃ under a load of 1.2 kg in accordance with ASTM D1238 test time, the composition exhibits about 10 g / 10 minutes or less, a melt flow index; whereby said support material by applying an alkaline solution to dissolve away from the three-dimensional object.
36.根据权利要求35所述的方法,其中所述支撑材料进一步包括增塑剂。 36. The method according to claim 35, wherein the support material further comprises a plasticizer.
37.根据权利要求35所述的方法,其中所述支撑材料表现出约100℃或更高的玻璃化转变温度。 37. The method according to claim 35, wherein the support material exhibits about 100 ℃ or higher glass transition temperature.
38.在一种通过将可固化材料沉积到基底上制造三维物体的方法中,其改进包括:提供含有羧酸的聚合物作为所述可固化材料,其中所述组合物可溶于碱性溶液中,并且其中当在230℃在1.2千克的负载下根据ASTM D1238进行测试时,所述组合物表现出约10克/10分钟或更小的熔体流动指数。 38. In one curable material deposited by the method of manufacturing a three-dimensional object on a substrate, the improvement comprising: providing a polymer comprising a carboxylic acid as the basic solution of the curable material, wherein said composition is soluble and wherein when at 230 ℃ according to ASTM D1238 when tested, the combination under a load of 1.2 kg was exhibited about 10 g / 10 min or less melt flow index.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102548738A (en) * 2009-09-30 2012-07-04 斯特拉塔西斯公司 Consumable materials having topographical surface patterns for use in extrusion-based digital manufacturing systems
CN103189187A (en) * 2010-11-01 2013-07-03 株式会社其恩斯 Modeling material for forming photoshaped article by ink-jet photoshaping method, support material for shape supporting during formation of photoshaped article by the photoshaping method, and process for producing photoshaped article by the photoshap
CN103189187B (en) * 2010-11-01 2015-09-02 株式会社其恩斯 The method of manufacturing a support material in an ink jet printing method for forming a three-dimensional shape of a light material processing model, in the light processing support for optical processing model shape and light processing model
CN103395209A (en) * 2013-08-08 2013-11-20 西安非凡士机器人科技有限公司 Large 3D printer based on FDM principles

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